Soluble compositions containing a 2, 5-dimercapto-1, 3, 4-thiadiazole derivative



SOLUBLE COMPOSITKONS CON'HAMNG A 2,5-DI- MERCAP'IO-1,3,4-THIADIALZOLE DERIVATIVE Edward N. Roberts, Hammond, lath, Ellis K. Fields, Chicago, and John S. Brown, Flossmoot," HIL, assignors to Standard Oil Company, Chicago, llh, a corporation of Indiana No Drawing. Applicationhehruary 27, 1953,

Serial No.

17 Claims. (Cl. 1452- -3339 This invention relates to improvements in soluble oil compositions and more particularly relates to soluble oil compositions having improved bactericidal, rust-inhibiting and stability properties.

Soluble oils are homogenous compositions containing as principal ingredients hydrocarbon oils and an emulsifying agent and smaller amounts of other components to impart various specific properties to the soluble oil composition. The components and their relative proportions are carefully chosen to achieve a balanced clear stable composition which will disperse on contact with water to form a fine stable millelilte emulsion.

The soluble oils have many uses which are well known to the art. One of the most important uses is as lubrieating and cooling agents in the cold working of metals, such as in grinding, Cutting and threading operations. For this use the soluble oil is dispersed in from about 10 to about 80 or more times its own volume of water and circulated over the contact point of the working tool and the metal being worked on. Frequently, difiiculty is encountered in this type of operation due to the tendency of the soluble oil emulsion or dispersion to cause rusting of metals in contact with such emulsions, particularly ferrous metals, and also because in the course of time these emulsions or dispersions develop strong, putrid, undesirable odors. Heretofore it has been the practice to overcome such trouble by incorporating in soluble oil compositions, among other ingredients, a bactericide and a suitable rust-inhibitor.

It is an object of the present invention to provide an improved soluble oil composition having bactericidal and rust-inhibiting properties. Another object of the invention is to provide a soluble oil composition having incorporated therein as a single component a compound exhibiting bactericidal and rust-inhibiting properties. Still another object of the invention is to provide a soluble oil composition which is stable and which will inhibit the growth of bacteria and the development of rust. A further object of the invention is to provide a soluble oil emulsion which is stable and non-rusting to ferrous metal and which exhibits bactericidal properties. Another object of the invention is to provide a method of inhibiting rusting and bacteria growth in soluble oil compositions. Other objects and advantages of the invention will become apparent upon the following description thereof.

In accordance with the present invention, the foregoing objects can be attained by providing a soluble oil composition comprising essentially from about 50% to about 90% of a hydrocarbon oil, from about to about 40% of an emulsifying agent, and from about 0.5% to about of an oil-soluble reaction product of an aldehyde, a mercaptan, and 2,5-dimercapto-1,3,4- thiadiazole in the molar ratio of from 2:2:1 to 10:2:9, and preferably in the molar ratio of 222:1. For brevity,

the reaction product will be referred to hereinafter as the 1,3,4-thiadiazole derivative.

In general, the reaction is carried out by adding an aldehyde to a mixture of the mercaptan and the dimercapto-thiadiazole, and heating the mixture at temperatures of from about 40 C. to about 140 period of from 20 minutes to about 16 hours. Preferably, the reaction is carried out in the presence of a suitable solvent, such as by way of example, dioxane, ethylene glycol, dimethyl and diethyl ethers, and diethylene glycol dimethyl and diethyl ethers. At the end of the reaction period the solvent and the water produced in the reaction areremoved from the reaction product, preferably by stripping in a vacuum, and the stripped product filtered if necessary.

The aldehyde employed may be an aliphatic, an aromatte, or a heterocyclic aldehyde of from about 1 to about 20 or more carbon atoms, and may contain substituents, such as alkoxy, hydroxy, alkyl mercapto, halogen or mtro groups. Examples of suitable aldehydes are formaldehyde, acetaldehyde, benzaldehyde, Z-ethylhexyl aldehyde, butyraldehyde, heptaldehyde, caprylic aldehyde, acryhcaldehyde, crotonaldehyde, vinyl acetaldehyde, phenyl acetaldehyde, nitrobenzaldehyde, salicylaldehyde, furfural, chloral, etc. Of the aldehydes, the aliphatlc aldehydes, particularly the low molecular weight aldehydes, such as formaldehyde, are preferred.

Any mercaptan can be employed in the reaction, althoughaliphatie or aromatic monoor polymercaptans containing from about 1 to about 30 carbon atoms, and preferably from about 6 to about 20 carbon atoms, are preferred. For bacteria growth control, better results are usually obtained with aliphatic mercaptans of from about 8 to about 12 carbon atoms. Examples of suitable mercaptans are ethyl mercaptan, butyl mercaptan, hexyl mercaptan, octyl mercaptan, nonyl mercaptan, octadecyl mercaptan, thiophenol, etc.

Although the herein-described thiadiazole derivatives all exhibit, to a definite degree, anti-rust properties, E. P. properties and bacteria growth control properties, all are not necessarily equivalent in their effectiveness, since, depending upon the nature and severity of the service in which thy are used, some variation in effectiveness may be exhibited.

The preparation of the above-described reaction products is illustrated by the following examples, which are given by way of illustration and are not intended to limit the scope of the invention.

' EXAMPLE I follows Per cent Carbon 44.22 Hydrogen 6.35 Sulfur 37.0 Nitrogen 7.9

EXAMPLE H To a solution of 45 grams (0.3 mol.) of 2,5dimercapto-1,3,4-thiadiazole and 121.2 grams (0.6 mol.) of tertiary dodecyl mercaptan in 200 cc. dioxane, heated to 5 C. was added, drop-wise, 49.5 cc. 36% aqueous formaldehyde over a twenty-minute period. The mixture was stirred for two and one-half hours at C., stripped in vacuo and filtered through celite. A yield of 154 grams of a viscous yellow product was obtained which analyzed as follows:

Percent Carbon 56,16 Hydrogen 836 Sulfur 26.9 Nitrogen 4.63

C. for a.

' of reaction, and filtered through celite.

EXAMPLE HI EXAMPLE IV mixture of 45 grams (.3 mol.) 2,5-dimercapto-l,3,4-

' thiadiazole and 102 cc. (.6 mol.) tertiary octyl mercaptan Was'stirred at 90 C. and treated drop-wise With 61 cc. benzaldehyde over a thirty-five minute period. The mixture 'was stirred at 100 C. for two hours, stripped m vacuo and filtered through celite plus a little alumina. The product, 175 grams, was a very VlSCOUS yelloworan eliquid completely soluble in naphtha. The prod uct c ontain'ed 27.4% sulfur and 4.9% nitrogen.

"EXAMPLE v 50cc. of furfural (.6 mol.) was added, drop-wise, to

'a mixture of 102cc. (.6 mol.) tertiary octyl mercaptan and 45 grams (.3'mol.) 2,5-dimercapto-1,3,4-thiadiazo1e and the mixturestirred for two hours at a temperature of 90 C. The reaction product was then stripped lll vacuo and filtered while warm. The product, 120 grams, was a dark purple viscous material having a sulfur content of 25.1% and a nitrogen content of 4.4%.

. EXAMPLE VI .,.,To astincd mixture of 41 cc. (.4 mol.) thiophenol and30. grams (.2 mol.) 2,5-dimercapto-1,3,4-thiadiazole at 75 80 C. was added 56 cc. 0.4 mol.) heptaldehyde, drop-wise, over a fifteen-minute period. St rring was continued for two hours at 100 C. The mixture was stripped at 120 C. and 4 millimeters pressure, then filtered hot through a little celite. The product, 94 grams,

was a viscous orange oil.

Instead of reacting 2,5-dimercapto-1,3,4-thiadiazole with the mercaptan and aldehyde as above-described in the re aration of the additive, we may earry out the ijreaciior? by forming in site the dlmercapto-thradlazole and reacting the same with the aldehyde and .mercaptan as illustrated by the following example:

"Lnvn To a mixture of 150 grams of cracked ice and 130.5 cc. of 84% hydrozine hydrate was added 280 cc. of carbon disulfide over a period of ten While cooling the mixture externally, a s "a grams of sodium hydroxide in 325 cc. of water and or ethyl alcohol was added, drop-wise, to the cooled tnrewhrle mamtaining a temperature of about 50 C. or lower. The mixture was then stirred and refluxed at 85 C. for three hours, cooled and acidified with 120 cc. of concentrated sulfuric acid diluted with 200 grams of ice. To the resulting slurry of 2,5-dimercapto-1,3,4-th1ad1a2qle in sodium sulfate solution was added 1000 c c. of tertiary octyl mercaptan, and then with vigorous agitation was added, drop-wise, 374 cc. of 37% aqueous formaldehyde. The resultant mixture was heated at 85 C. tor two hours and cooled to room temperature (about 23 (3.). The mix- .ture separated into a lower solidified layer of sodium sulfate and an upper liquid layer. The latter was decanted, treated with grams of sodium bicarbonate, then stripped in vacuo and filtered throughcel ite; 610 grams of a light yellow liquid product was obtained.

In'formulating the soluble oil composition the base oil can be any hydrocarbon oil, such as a mrner'ol Qll, of suitable viscosity. Usually, hydrocarbon 0118 having a Saybolt viscosity in the range from about 75 seconds to about 350 seconds at 100 F. are preferred, although, depending upon the intended use, hydrocarbon oils .having a Saybolt viscosity upwards of about 60 seconds at 100 F. can be employed.

The emulsifying agents used in the tormulation of soluble oil compositions are preferably alkali metal soaps, or ammonium soaps of preferentially oil-soluble sulfonrc acids obtained in the treatment of hydrocarbon oils with strong or fuming sulfuric acid. The preferentially 011- soluble petroleum sulfonic acids, commonly referred to as mahoganyacids because of their reddish-brown color, arewell known in the art. These sulfonic acids are obtained by treating petroleum distillatesof between about 50 to about 100 seconds Saybolt Universal viscosity at 100 F. with between about 3 to 9 pounds, and

preferably between 3 and 6 pounds, of concentrated or fnmingsulfuric acid per gallon of oil. After removal of the sulfuric acid sludge the acid-treated oil is extracted with a suitable aliphatic alcohol of about 60% strength to remove the preferentially oil-soluble petroleum sulfonic acids. The alcoholic fraction containing the sulfonic acid is thenneutralized with a desired neutralizing agent, such as for example, sodium or potas-' sium hydroxide orammonia, the mixture allowed to' settle, and the alcohol layer containing the mahogany acid soap drawn'ofi. "The alcohol is then removed by'distillation under vacuum. To facilitate'handling, the'soaps are preferably dissolved in a petroleum oil to give a blend containing between 35% The molecular weights of the'jpreferentially oil-soluble sulfonic acids obtained in the acid treatment of petroleum oils vary from about 420 to about 500, depending upon the petroleum oil treated and the amount of sulfuricacid employed. While any one of the preferentially oil-soluble sulfonic acids can be used, we prefer to use those acids having molecular weights within the range of'410 to 450, although can be used.

In formulating soluble oil compositions it is frequently desirable to use in combination with the mahogany soaps other emulsifying agents or surface-active agents. For example, the mahogany soaps can-be used in combination with potassiumor sodium rosin soap or non-ionic surface-active agents, such as for example, polyoxyethylene sorbitan esters of mixed fatty and resin acids. A suitable ester of this type is a product marketed by the Atlas Powder Company as G8916- T. Inaddition to the basic components of soluble oil compositions, namely, the emulsifying agent and the hydrocarbon oil, other constituents are'usually included, such as an alcohol, for example, isopropyl alcohol, ethyl alcohol, etc., oleic acid,

mono-, diortri-ethanolamine, and usually a small amount of water suflicient to maintain the balance of the various components. For certain types'of services, it

is often the practice to incorporate in soluble oil'compc sitions an extreme pressure agent, suchas for example, sulfurized fatty oils, sulfurized sperm oil, or other organic compounds containing active sulfur, as well as chlorinated organic compounds. Chip settling agents, such as a hydroxy aromatic acid, for example, tannic acid, of the type claimed in copending Cafcas et a1. application Serial Number 106,488 filed July 23, 1949, now U. S. 2,668,146, issued February 2, 1954, can also be incorporated in the soluble oil composition. a

There are many soluble oil formulations known to the art and the present invention is not limited to the addition of the herein-described thiadiazole derivatives to any particular soluble oil base, but is applicable to the use of such thiadiazole derivatives to any basic soluble oil formula, for example, any of those of the following patents: Hughes 1,577,723; Johnson 1,619,074; Merrill 1,739,686; Adams 1,871,940; Strauch 1,909,080; Butts 1.979,250; Adams et a1. 2,039,377; Adams et al. 2.243,994; Fabian et al. 2,097,085; Waugh 2,552,913, and others.

Illustrative of soluble oil formulations in which the herein-described thiadiazole derivatives are employed are' the following examples, which are given only by way of illustration:

EXAMPLE A Percent Sodium mahogany soap blend (50% soap-50% Polyoxyethylene sorbitan ester of mixed fatty and resin ncldsmarketed by Atlas Powder Company as G-8918-T.

Reaction product of Example I.

and about 50% soap.

soaps of mixtures of lower mo-' lecnlar weight ,sulfomc acids and higher sulfonic acids- Example Example D Percent Percent Sodium Mahogany Soap 18. 8 24. 7 Sodium Rosin Soap 3. 3. 4 Ethanol 1.3 0.5 Water 0. s 0. 5 48 lie-caustic Soda 0. 09 0. 07 Thiediazole Derivative I I 1. 8 1. 9 Petroleum Oil. 73. 71 17. 3 Petroleum 011 L... 51. 03

1 Reaction Product of Example I. I set; at 100 F.--80. SSU at 100 F.1e0.

EXAMPLE Id 1 1 Per cent Sodium mahogany soap 16% Triethanolamme as uuuuuuuu w 0. 5 Tannic acid .N 1.7;]! Oleic acid 0.; Ethanol 0.l Petroleum oil '78. Thiadiazole derivative a- 1.8 In each of the above formulations, derivative can be any of the herein-disclosed r oducts of 2,5-dimercapto-1,3,4-thiadiaz0ie, a i' and an aldehyde, such as for example, those d cribed in Examples I to VIII, supra. Also, depending; the particular use and other conditions, the amount or thiadiazole derivative used in the above formulations can be varied from about 0.05% to about 10%.

While it is preferred to incorporate the herein-described thiadiazole derivatives in thesoluble o l, it is, of course, possible to add the same to the dispersion of the soluble oil in water. t

The efiectiveness of the herein-described thiadiazole derivatives in inhibiting bacteria growth, resting and in stabilizing emulsions is described by the a in table I, below. These data were obtained by r b emulsions of one part soluble oils with and 40 rts heav ly contaminated water containing dirt, fungi and bacteria, adding iron chips to the emulsions and air-blowing the emulsion for about five days at about /2l to 80 F. Bacterial counts were taken at the end or this time and the condition of the emulsion and iron chips noted. The

following samples were subjected to the foregoing test: Sample A.Example A without the thiadiazole derivative.

Sample B.-Exa.mple A. Sample C.--Example B. 1 n

Sample D.-Example C without the thiaoiazole derivative.

Sample E.Example C.

Tan, no sludge or rust. Tun, slight sludge and rust.

Heavy sludge and rust.

Light colored emulsion, no

slllgge or rust.

The data show that the herein-described tl iiadiazole derivatives are effective bactericides and fungicides, keep the iron chips from rusting, and prevent, the emulsion from sludging.

The 'ability of the herein-described thiadiazole derivativesto prevent seizure and welding o metal surfaces tive.

Sample G.Example D.

Table II Almen Sample (10:1 Emulsion) Pass Fail '1 he herein-described oil compositions can contain, in addition to the herein-named components, other additives, such as other oiliness agents, anti-oxidants, additional E. P. agents, bactericides, etc.

Percentages given herein and in the appended claims are weight percentages unless otherwise specified.

The herein described oil-soluble reaction products of an aldehyde, a mercaptan and 2,5-dimercapto1,3,4-thia uiazole are claimed as such and in oleaginous-compositions in copending E. K. Fields application Serial No. 318,091 filed October 31, 1952.

While the present invention has been described by reference to specitic embodiments thereof, these are given by way or illustration only, and the invention is not to be limited thereto, but includes within its scope such modifications and variations as come within the spirit of the appended claims.

We claim:

1. An emulsifiable soluble oil composition comprising a major proportion of a hydrocarbon oil, an emulsifying agent, and from about 0.5% to about 10% of the oilsoluble reaction product of an aldehyde, a mercaptan selected from the class consisting of an aliphatic triercaptan and an aromatic mercaptan, and 2,5-dimercapto- 1,3,4-thiadiazole, said aldehyde, mercaptan and 2,5-dimercapto-l,3,4-thiadiazole being reacted in. the molar ratio of from 2:2:1 to 10:2:9.

2. A soluble oil composition as described in claim 1 in which the aldehyde is an aliphatic aldehyde of from about 1 to about 20 carbon atoms.

3. A soluble oil composition as described in claim 2 in which the aliphatic aldehyde is formaldehyde.

4. A soluble oil composition as described in claim 2 in which the aliphatic aldehyde is Z-ethylhexaldehyde.

5. A soluble oil composition as described in claim 1 in which the aldehyde is an aromatic aldehyde.

6. A soluble oil composition 'as described in claim 5 in which the aromatic aldehyde is benzaldehyde.

7. A soluble oil composition as described in claim 5 in which the aromatic aldehyde is salicylaldehyde.

8. A soluble oil composition described in claim 1 in which the aldehyde is a heterocyclic aldehyde.

9. A soluble oil composition as described in claim 8 in which the heterocyclic aldehyde is furfural.

10. A soluble oil composition as described in claim 1 in which the mercaptan is octyl mercaptan.

11. A soluble oil composition as described in claim 1 in which the mercaptan is dodecyl mcrcaptan.

12. A soluble oil composition described in claim 1 in which the mercaptan is thiophenol.

13. An emulsifiable soluble oil composition comprising a major proportion of a hydrocarbon oil, from about 5% to about 40% of an alkali metal salt of a preferentially oil-soluble sulfonic acid, and from about 0.5% to about 10% of an oil-soluble reaction product of formaldehyde, an aliphatic mercaptan having from about 8 to about 12 carbon atoms and 2,5-dimercapto-1,3,4- thiadiazole, said formaldehyde, aliphatic mercaptan and 2,5-diniercapto-1,3,4-thiadiazole being reacted in the molar ratio of from 2:2:1 to 10:2:9.

14. An emulsifiable soluble oil composition comprising a major roportion of a hydrocarbon oil, from about 5% to out40% sodium mahogany soap, and from about 0.5% to about 10% of an oihsoluble reaction product of formaldehyde, ociyl mercaptan and 2,5-dimercapto-1,3,4-thiadiazole, said formaldehyde, octyl mercaptan and 2,5-dimercapto1,3,4-thiadiazole being reacted in the molar ratio of from 212:1 to 10:2:9.

15. An emulsifiable soluble oil composition comprising a major proportion of a hydrocarbon oil, from about 5% to about 40% of sodium mahogany soap, and from about 0.5% to about 10% of an oil-soluble reaction 1,3,4-thiadiazo1e, in small but Si stantially inhibit bacteria growth in d dispersion, said dehyde, thiadiazole c mmpm and 25 roo being reacted m the molar ra 17. The method of inhibiting bacteria growth in emulsions of soluble portion of a hydrocarbon oil and an emuls' in a and the method of inhibiting corrosion of m al uri zfgs in contact with said emulsions, comprising. incorporating l in said soluble oil composition from about 0.57 to 10% of the oil-soluble reaction product of m ameigiig a mercaptan selected from the class consisting of an aliphatic mercaptan and an aromatic mercaptan and 2,5ldnneraagtg- 3,44hradizzgle,thlsaid aldehyde, mercapanan lmerca to- ,4- 'adi l 1n the molar ratio of fr m 2:2:1 to lifi y mcfed Reflex-emcee Ct at in the file oi this patent UNITED STATES PATENTS 20 2,154,096 Loane A 2,597,838 Lowe et al M 5 id; i322 2,607,737 wwama a a1 Aug. is, 1952 oil compositions. comprising a major pro- '1 

1. AN EMULSIFIABLE SOLUBLE OIL COMPOSITION COMPRISING A MAJOR PROPORTION OF A HYDROCARBON OIL, AN EMULSIFYING AGENT, AND FROM ABOUT 0.5% TO ABOUT 10% OF THE OILSOLUBLE REACTION PRODUCT OF AN ALDEHYDE, A MERCAPTAN SELECTED FROM THE CLASS CONSISTING OF AN ALIPHATIC MERCAPTAN AND AN AROMATIC MERCAPTAN, AND 2,5-DIMERCAPTO1,3,4-THIADIAZOLE, SAID ALDEHYDE, MERCAPTAN AND 2,5-DIMERCAPTO-1,3,4-THIADIAZOLE BEING REACTED IN THE MOLAR RATIO OF FROM 2:2:1 TO 10:2:9. 